System and method for using a voc free low radiant flux led uv curable composition

ABSTRACT

The present invention generally relates to a system and method for using a volatile organic compound (VOC) free low radiant flux LED UV curable composition, and more particularly to unique and novel uses of the composition such as one or two or more of a fire retardant, clear coat, composite material, resin, top coat, improved holdout coating, a sealant coat, and combinations of the same.

The present application claims the benefits of and priority, under 35U.S.C. § 119(e) to U.S. Provisional Patent Application No. 62/335,823filed May 13, 2016, the present application further claims the benefitsof and priority, under 35 U.S.C. § 119(e), to U.S. ProvisionalApplication Ser. No. 62/382,968 filed Sep. 2, 2016, the presentapplication further claims the benefits of and priority, under 35 U.S.C.§ 119(e), to U.S. Provisional Application Ser. No. 62/413,199 filed Oct.26, 2016, the present application further claims the benefits of andpriority, under 35 U.S.C. § 119(e), to U.S. Provisional Application Ser.No. 62/430,125 filed Dec. 5, 2016, and also claims the benefits of andpriority, under 35 U.S.C. § 119(e), to U.S. Provisional PatentApplication No. 62/452,093 filed Jan. 30, 2017, each of theabove-identified provisional patent applications are hereby fullyincorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to a system and method for usinga volatile organic compound (VOC) free low radiant flux LED UV curablecomposition, and more particularly to unique and novel uses of thecomposition such as one or two or more of the following a fireretardant, clear coat, composite material, resin, top coat, improvedholdout coating, a sealant coat, and combinations of the same.

DISCUSSION OF THE BACKGROUND

Radiation curable compositions are beginning to gain industryacceptance. In order to cure radiation curable coatings high radiantfluxes are required on the order of 5 W/cm² or higher at the surface.These high radiant fluxes are typically generated with high flux energysources including electron beam energy sources, mercury vapor lightenergy sources, which emit radiation in radiation including ultravioletA (UVA) radiation (315 nm to 400 nm), ultraviolet B (UVB) radiation (280nm to 315 nm), ultraviolet C (UVC) radiation (100 nm to 280 nm), andinfrared (IR) radiation (700 nm to 1000 nm). Moreover, these highradiant flux energy sources are dangerous and require UV shielding toprotect the operator and passerby's from UV light. Finally, the highradiant flux energy sources cannot be used with temperature sensitivesubstrates, e.g., substrates that are sensitive to high temperatures.

Besides the high radiant fluxes required to cure conventional radiationcurable compositions. The conventional radiation curable compositionscannot cure to be tack free and are tacky after radiation curable due tooxygen inhibition. In practice, this requires using a nitrogen blanketin order to properly cure these UV compositions.

A need exists for a system and method for using VOC free low radiantflux LED UV curable composition.

SUMMARY OF THE INVENTION

Accordingly, the invention is directed to a system and method for usingVOC free low radiant flux LED UV curable composition.

An advantage of the invention is to provide a coated substrate materialwith low radiant flux LED UV curable composition.

Another advantage of the invention is to provide a method of using a lowradiant flux LED UV curable composition.

Another advantage of the invention is to provide a method of using a lowradiant flux LED UV curable composition that cures in an oxygenenvironment at sixty seconds to tack free coating.

Still yet another advantage of the invention is to provide low radiantflux LED UV curable composition that has more than one use in a singlecoating.

Still yet another advantage of the invention is to provide low radiantflux LED UV curable composition that is a clear coat and fire retardant.

Still yet another advantage of the invention is to provide low radiantflux LED UV curable composition that is a clear coat and improvesholdout.

Still yet another advantage of the invention is one or more of fasterproduction speeds and capacity, reduction of work-in-process,dramatically reduced set-up/clean-up labor compared to related art,environmentally friendly, energy savings, no emissions controls, lessfloor space needed and increase yield and reduce scrap.

Still yet another advantage of the invention is to provide a coatedsubstrate or article where the coated article includes a cured coatingthat has one or more of the following attributes: it is a chemicallyresistant coating, a sealant coating, a non-permeable coating, a fireretardant coating, an improved holdout coating, a tack free coating, anda pigmented coating.

One embodiment is directed towards a method of using volatile organiccompound (VOC) free low radiant flux UV curable composition as a fireretardant coating to improve a fire retardant nature of a substrate. Themethod includes applying the VOC free low radiant flux UV curablecomposition on the substrate to form a fire retardant coating andapplying an energy source having a wavelength in a range from about 360nm to about 420 nm and a radiant flux at the surface of the coating ofabout 100 mW/cm² or less to cure the fire retardant coating within about120 seconds or less.

Additional features and advantages of the invention will be set forth inthe description which follows, and in part will be apparent from thedescription, or may be learned by practice of the invention. Theobjectives and other advantages of the invention will be realized andattained by the structure particularly pointed out in the writtendescription and claims hereof as well as the appended drawings.

The preceding is a simplified summary of the disclosure to provide anunderstanding of some aspects of the disclosure. This summary is neitheran extensive nor exhaustive overview of the disclosure and its variousaspects, embodiments, and/or configurations. It is intended neither toidentify key or critical elements of the disclosure nor to delineate thescope of the disclosure but to present selected concepts of thedisclosure in a simplified form as an introduction to the more detaileddescription presented below. As will be appreciated, other aspects,embodiments, and/or configurations of the disclosure are possible,utilizing, and alone or in combination, one or more of the features setforth above or described in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included to provide a furtherunderstanding of the invention and are incorporated in and constitute apart of this specification, illustrate embodiments of the invention andtogether with the description serve to explain the principles of theinvention.

In the drawings:

FIG. 1A illustrates a top view of a damaged article according to anembodiment of the invention;

FIG. 1B illustrates a cross sectional view along line A to A′ of thedamaged article of FIG. 1A;

FIG. 1C illustrates a cross sectional view along line A to A′ of therepaired article of FIG. 1A;

FIG. 1D illustrates a top down view of the repaired article;

FIG. 2A illustrates a top view of a damaged article according to anotherembodiment of the invention;

FIG. 2B illustrates a cross sectional view along line A to A′ of thedamaged article of FIG. 2A;

FIG. 2C illustrates a cross sectional view along line A to A′ of therepaired article of FIG. 2A;

FIG. 2D illustrates a top down view of the repaired article;

FIG. 3A illustrates a top view of a damaged article according to anotherembodiment of the invention;

FIG. 3B illustrates a cross sectional view along line A to A′ of thedamaged article of FIG. 3A;

FIG. 3C illustrates a cross sectional view along line A to A′ of therepaired article of FIG. 3A;

FIG. 3D illustrates a top down view of the repaired article;

FIG. 4 illustrates a method of repair according to an embodiment of theinvention;

FIG. 5 illustrates a method of forming a composite apparatus accordingto an embodiment of the invention;

FIG. 6 illustrates a method of resurfacing a swimming pool or spaaccording to an embodiment of the invention;

FIG. 7 illustrates a method of repairing a pipe or pipeline according toan embodiment of the invention;

FIG. 8 illustrates an acrylate conversion versus time at various lowradiation fluxes according to Example 4;

FIG. 9 illustrates an acrylate conversion versus time at various lowradiation fluxes according to Example 4;

FIG. 10 illustrates an acrylate conversion versus time at various lowradiation fluxes according to Example 4; and

FIG. 11 illustrates an acrylate conversion versus time at various lowradiation fluxes according to Example 4.

In the appended figures, similar components and/or features may have thesame reference label. Further, various components of the same type maybe distinguished by following the reference label by a letter thatdistinguishes among the similar components. If only the first referencelabel is used in the specification, the description is applicable to anyone of the similar components having the same first reference labelirrespective of the second reference label.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

The disclosure can provide a number of advantages depending on theparticular aspect, embodiment, and/or configuration. These and otheradvantages will be apparent from the disclosure.

The phrases “at least one,” “one or more,” and “and/or” are open-endedexpressions that are both conjunctive and disjunctive in operation. Forexample, each of the expressions “at least one of A, B and C,” “at leastone of A, B, or C,” “one or more of A, B, and C,” “one or more of A, B,or C” and “A, B, and/or C” means A alone, B alone, C alone, A and Btogether, A and C together, B and C together, or A, B and C together.

The term “a” or “an” entity refers to one or more of that entity. Assuch, the terms “a” (or “an”), “one or more” and “at least one” can beused interchangeably herein. It is also to be noted that the terms“comprising,” “including,” and “having” can be used interchangeably.

The term “automatic” and variations thereof, as used herein, refers toany process or operation done without material human input when theprocess or operation is performed. However, a process or operation canbe automatic, even though performance of the process or operation usesmaterial or immaterial human input, if the input is received beforeperformance of the process or operation. Human input is deemed to bematerial if such input influences how the process or operation will beperformed. Human input that consents to the performance of the processor operation is not deemed to be “material.”

Embodiments herein presented are not exhaustive, and further embodimentsmay be now known or later derived by one skilled in the art.

Embodiments of the invention are directed towards using a VOC free lowradiant flux UV curable material. In one embodiment the VOC free lowradiant flux UV curable material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiators and aradical inhibitor. Optional additional components may includeglass/silica fillers and pigments. Optionally, a thermal initiator canalso be added to promote the curing of the material. Thermal initiatorsare known in the art.

The VOC free low radiant flux UV curable material can be cured into atack free coating cured with UV or visible light irradiation fromrelatively low intensity light sources within sixty seconds or less andin wavelength in range from about 355 nm to about 420 nm. The materialcan be cured without UVB radiation and UVC radiation. In a preferredembodiment, the wavelength is from 385 nm to 405 nm and a more preferredembodiment the wavelength is about 390 nm. Low radiant flux means anenergy measured at the surface of the material to be cured of less thanabout 500 mW/cm².

In a preferred embodiment, the low radiant flux means the energy fromthe energy source at the surface of the material to be cured is lessthan 400 mW/cm², in a more preferred embodiment, the energy at thesurface of the material to be cured is less than 300 mW/cm², in a morepreferred embodiment, the energy at the surface of the material to becured is less than 200 mW/cm², in a more preferred embodiment the energyat the surface of the material to be cured is less than 100 mW/cm², andin a most preferred embodiment, the energy at the surface of thematerial to be cured is less than 40 mW/cm². In another embodiment, thelow radiant flux is the energy at the surface of the material to becured is 20 mW/cm², 19 mW/cm², 18 mW/cm², 17 mW/cm², 16 mW/cm², 15mW/cm², 14 mW/cm², 13 mW/cm², 12 mW/cm², 11 mW/cm², 10 mW/cm², 9 mW/cm²,8 mW/cm², 7 mW/cm², 6 mW/cm², 5 mW/cm², 4 mW/cm², 3 mW/cm², 2 mW/cm², or1 mW/cm².

In one embodiment, the energy source can be adjusted or controlled suchthat low radiant flux at the surface of the material to be cured isvariable, e.g., linearly ramped from high to low or vice versa,non-linearly ramped or a combination of linearly ramping and non-linearramping from about 0 mW/cm² to about 400 mW/cm² over a specified time orgreater. Optionally and/or alternatively, the radiant flux may beintermittent by pulsing the energy source such that the energy atsurface is on and off for predetermined time intervals. The predeterminetime internals may be from 1 nanosecond to 5 seconds or more. This iscan aid the curing of VOC free low radiant flux UV curable material asthe curing process is a photochemical exothermic process. When using atemperature sensitive substrate one may want to minimize the temperatureon the substrate caused by the exothermic curing and in such casepredetermined wait time internals and applied time internals of theradiation can be configured to minimize temperature caused by theexothermic curing.

In one embodiment, the VOC free low radiant flux UV curable material haszero VOCs. The material cures rapidly to form a glassy high modulusoptically clear material for example, the material may cure in twominutes or less. In a preferred embodiment, the material cures inone-hundred twenty seconds or less. The cured material is excellent foruse in protective coatings, optical and outdoor applications and isnon-yellowing when cured and has low oxygen inhibition. In oneembodiment, the VOC free low radiant flux UV curable material isavailable from CPS 1020, CPS 1027, CPS 1030, and CPS 1040 from ColoradoPhotopolmyer Solutions out of Boulder Colorado, BlueSky Armor™ 1007Clear Top Coat, BlueSky Armor™ 1027 Clear Top Coat, BlueSky Armor™ 1047Clear Knife Grade Filler, BlueSky Armor™ 1057 Laminating Resin from MSICoatings, Inc. out of Boulder, Colorado. In one embodiment, the VOC freelow radiant flux UV curable material is solvent free (100% solids).

Optionally and/or alternatively, the VOC free low radiant flux UVmaterial described herein in various embodiments can be any sheenincluding but not limited to a gloss sheen, a semi-gloss sheen, a satinsheen, a flat sheen, and an egg shell sheen.

The acrylate monomer may include monomers as known in the art, e.g., oneor more of ethylene glycoldi(meth)acrylate,tetraethyleneglycol-di(meth)acrylate, poly(ethyleneglycol)dimethacrylates, the condensation product of bisphenol A andglycidyl methacrylate, 2,2′-bis4-(3-methacryloxy-2-hydroxypropoxy)-phenyl]propane, hexanedioldi(meth)acrylate, tripropylene glycol di(meth)acrylate, butanedioldi(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, allyl (meth)acrylate trimethylolpropanetriacrylate, tris(2-hydroxy ethyl) isocyanurate triacrylate,tricyclodecane dimethanol diacrylate, and combinations thereof.

The thiol monomer/oligomers may include thiol monomer/oligomers as knownin the art, e.g., one or more of, ethylene glycol bis(thioglycolate),ethylene glycol bis(3-mercaptopropionate), pentaerythritoltetra(3-mercaptopropionate), trimethylolpropanetris(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate),trimethylolpropane tris(2-mercaptoacetate), 1,6-hexanedithiol,1,2-benzenedithiol, 1,3-benzenedithiol, isophorone diurethane thiol, andcombinations thereof.

The photo initiators may include photo initiators as known in the artthat are capable of generating free radicals when exposed to visiblelight and/or UVA radiation. A preferred class of photo initiator isbisacyl phosphine oxides. In addition, the photo initiator may includeone or more of 2,2-dimethoxy-1,2-diphenylethan-1-one,bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), 1-hydroxycyclohexylbenzophenone, trimethyl-benzoyl-diphenyl-phosphine-oxide, andcombinations thereof.

The radical inhibitors may include radical inhibitors as known in theart, e.g., one or more of N-nitrosophenylhydroxylamine, hydroquinone andderivatives, monomethyl ether hydroquinone, benzoquinone, methoxyhydroquinone, tert butyl catechol, phenothiazine, or pyrogallol. In oneaspect, the inhibitors prevent the acrylate monomer photopolymerizationfrom occurring before being activated by light.

The glass/silica fillers may include glass/silica fillers as known inthe art, e.g., one or more of a silica particle, Kevlar veil, PET mesh,fiber mesh, metal mesh, Multi-Walled Carbon NanoTube (MWCNTs), CarbonNanoTube (CNTs), fumed silica particle, organoclay, clays, alumina,—Mania, zirconia, carbon, bioglass (or bioactive glass), hydroxyapatite(HA) particle/mesh, quartz, barium glass, barium salt, and titaniumdioxide. Optionally and/or alternatively, additional additives may beincluded including anti-skid powder configured to prevent slipping onthe surface, e.g., a roughened surface. The anti-skid coatings mayinclude additives for anti-slip purposes, e.g., silica, polyesterpowders, sand, organic or synthetic rigid particles, and combinations ofthe same.

The pigments may include pigments as known in the art, e.g., titaniumdioxide, zinc phosphate, zinc sulfide, zinc oxide, barium sulfate,magnesium silicate and corrosion inhibiting pigments, e.g., strontiumchromate, zinc phosphate and barium metaborate, can be included.Optionally and/or alternatively, the pigment may be added to the desiredcolor, e.g., up to 5% by volume to create a transparent tone to a solidcolored coating. Several coatings may be necessary for adequate coverageand desired thickness.

In one embodiment, the pigments can include any combination of pigmentsto achieve any color, e.g., UVDJ070 Spectraray IJ as a white pigment,UVDJ107 Spectraray IJ as a black pigment, UVDJ554 Spectraray IJ as acyan pigment, UVDJ32 Spectraray IJ as a red and/or magenta pigment,and/or a UVDJ350 Spectraray IJ as a yellow pigment.

In one embodiment the VOC free low radiant flux UV curable material mayhave a viscosity [cps] at 25 C in a range from about 20 [cps] to about1,000,000 [cps] or more, and in a preferred embodiment the viscosity 30[cps] to 300 [cps] or more.

The VOC free low radiant flux UV curable composition may be in any formincluding for example, pre-impregnated composite fiber, pre-impregnatedsheets or rolls, sprayable, paintable, laminating, paste, rollable, andmoldable varieties of viscosity.

One embodiment of the invention is directed towards a method of usingthe VOC free low radiant flux UV curable material according to methodsdescribed herein as decorative and/or protective coating on interior andexterior surfaces of: aircraft, automotive, recreational vehicles,watercraft, furniture and cabinetry, hardwood flooring, such as solidand engineered laminates, fishing tackle such as coating lures andbaits, fiber reinforced fishing rods, fiber reinforced water sportsequipment such as but not limited to: surfboards, wakeboards,bodyboards, water skis, skim boards, paddle boats, etc., fiberreinforced bathware, spas, and hot tubs, fiber reinforced body panelsfor automotive, recreational vehicles, and watercraft. As a laminatingresin, filling agent or coating for the manufacture and repair of:fishing tackle such as coating lures, baits, fiber reinforced fishingrods, fiber reinforced water sports equipment such as but not limitedto: surfboards, wakeboards, bodyboards, water skis, skim boards, paddleboats, etc., fiber reinforced bathware, spas, pools, hot tubs, fiberreinforced body panels for automotive, recreational vehicles,watercraft, vehicle paneling such as those for recreational vehiclecompartment walls, acoustic panels, aircraft interior cabinetry, fiberreinforced construction applications such as retention barriers forwindow wells, replications of construction facades such as decorativerock for building fronts, millwork, or ornamentations, structural chips,cracks, breaks, punctures or voids in composite matrix products,fiberglass, acrylic, glass, ceramic, porcelain, tile, natural, manmadestone, concrete, any solid material to add substance where material islacking creating a new surface to provide for continuity, restoration,repair, etc. that is sandable, paintable, and can be tooled andconformed.

One embodiment of the invention includes using the VOC free low radiantflux UV curable material as general purpose bonding material for two ormore materials such as securing the windings over the guide to the rodon a fishing rod, securing windings on a fishing fly, securingelectrical windings on motors, or any other process where the materialsto be bonded are both covered and irradiated. As an anti-tamperingcoating useful for indicating a break in safety protocols requiring thephysical security of an object within a storage container or device.

One embodiment of the invention includes using the VOC free low radiantflux UV curable material to form or improve at least one or more of atack free coating, low tack free cure time, rapid cure time, fireretardant coating, clear coating, volatile organic compound (VOC) freecoating, improved holdout composition, and combinations of the same.

One embodiment is directed towards a method of coating a substrate withthe VOC free low radiant flux UV curable material to form a glassy highmodulus, with non-yellowing and low oxygen inhibition coating.

One embodiment of the invention is directed towards a dual purposecoating including a top coat and fire retardant in one coating.

One embodiment is directed towards a method of using the VOC free lowradiant flux UV curable material as a coating for more than one purposeincluding two or more of: a top coat, a fire retardant coating, asealant coating, e.g., cement sealer, wood sealer, a stain coating, animproved holdout coating and combinations of the same.

One embodiment of the invention is directed towards cured coating with apencil hardness H in range from about 1H to about 6H or greater.

One embodiment of the invention is directed towards curing the VOC freelow radiant flux UV curable material to a cure depth in a range fromless than 1 mm to about 40 mm or less, in a preferred embodiment thecure depth is less than 1 mm. One embodiment of the invention isdirected towards filing cracks in concrete or similar material andcuring the material.

Holdout means the ability of a coating to remain at or near the surfaceof a substrate, as opposed to penetrating that substrate. Better holdoutresults in the appearance of a smoother, more uniform coated surfacewith increased gloss and depth as compared to a coated substrate withless holdout. This is true even though the same dry film thickness ofcoating may have been applied to both substrates. For instance, in aporous substrate, when a coating is applied, the coating may absorb orpermeate into the substrate. One embodiment of the invention is directedtowards a method that reduces the amount of the coating absorbed intothe substrate, allowing more of the coating to remain at or near thesurface of the substrate. By increasing holdout in this manner, theresulting substrate has a smoother overall surface, and the substraterequires a fewer number of coatings. By reducing the number of requiredcoatings, the invention also provides the advantages of reducing laborand material costs, while maintaining a coating with desirableproperties. Moreover, increased or improved holdout means decreasedfiber raising and increased moisture resistance. It is believed, thesubstrate will require a fewer number of coatings to achieve a desiredfinish. It is also believed the invention will lead to reducedprocessing time and reduced labor and material costs. Moreover, it isbelieved the invention provides a way to size a three-dimensionalsubstrate. It is further believed the substrate produced by the processof the invention will typically display an increased stiffness,strength, smoothness and/or weight. It is further believed the inventioncan produce a sized or pretreated board that is compatible with avariety of overcoats. In one embodiment, the invention is directedtowards man-made fiber boards, such as low density, medium density andhigh density fiber boards, for example.

Fire retardant or fire resistance means a coating with the ability towithstand fire. One quantification is the ability of the coating to passa twelve second or sixty second vertical flammability test as set forthin 37 C.F.R. Part 25.853 (a) Amdt 25-116 Appendix F Part I (a)(1)(ii),which is hereby incorporated by reference. As shown Example 1—Table 1 orExample 2—Table 2, therefore, having a dual purpose coating was a clearcoat and fire retardant.

One embodiment of the invention is directed towards using the VOC freelow radiant flux UV curable material as a fire retardant, sealant and atop coat finish in one coating. Therefore, having a triple purpose in asingle coating.

Tack free is the ability of a coating to not be sticky on the surface asopposed to coating that it is sticky on a surface. Tack free time isequal to or less than the curing time and means the applied coating isno longer sticky to the touch.

VOC free means a coating or coating composition that excludes organicchemicals, contains no organic chemicals, or has zero organic chemicalsthat have a high vapor pressure at ordinary room temperature. A highvapor pressure is a vapor pressure that results from a low boilingpoint, which causes large numbers of molecules to evaporate or sublimatefrom the liquid or solid form of the compound and enter the surroundingair, a trait known as volatility. For example, formaldehyde, whichevaporates from paint, has a boiling point of only −19° C. (−2° F.).

One embodiment of the invention is directed towards using the VOC freelow radiant flux UV curable material on a broad variety of substrates,made from various materials, such as wood, wood laminates, fiber glass,plastic, metal and combinations of the same. Examples of typicalsubstrates may be selected from the group including, but not limited to,substrates such as high density fiber board, medium density fiber board,low density fiber board, cardboard, chipboard, particle board,mini-blinds, Masonite, cement fiber board and mindy board.

In a preferred embodiment, the energy source can be a light emittingdiode (LED), fluorescent tube or other conventional bulb having awavelength in the range from about 360 nm to about 420 nm, in apreferred embodiment about 390 nm. In one embodiment, a LED BlacklightUltraviolet bar powered by 9×3-Watt UV long life LED's (approx. 50,000hrs.) and a low power draw of only 30-Watts, the Eco UV Bar 50 IR is anaffordable, low maintenance solution for producing brilliant washes ofultraviolet light that can be used. The energy source can be a handheldflashlight designed for LED bulbs below 420 nm, LED bar lights commonlyfound in the entertainment industry emitting below 420 nm, fluorescenttube lighting commonly available in the UV curing industry and/orexposure to ambient sunlight.

One embodiment is directed towards a method of resurfacing or coating amaterial or substrate. The material or substrate may be a preexistingmaterial including one or more of cement, wood, plater, plastic,fiberglass, thermoplastics, and combinations of the same. For example,the material may be worn or used swimming pool surface including atleast one or more of chips, cracks, mold, algae, and combinations of thesame. The resurfacing method includes cleaning and drying the cementsurface. The method includes applying a VOC free low radiant flux UVmaterial to the material or substrate by any conventional technique,e.g., spray, paint brush, roller, combinations of the same or the like,to a predetermined thickness. In a preferred embodiment, the thicknessof the wet coating is in a range from about 2 mils to about 5 mils.Next, an energy source having wavelength in a range from about 360 nm toabout 420 nm at a surface power density less than about 400 mW/cm² wasapplied to cure the material for about two minutes or less. Of course,other curing surface power densities, curing times and/or additives mayalso be utilized as described herein. These steps are repeated until thedesired thickness is achieved. Optionally, and/or alternatively, theenergy source may be dynamically adjusted as described herein, e.g., bepulsed, ramped non-linearly, ramped linearly or combination as describedherein.

One embodiment of the invention is directed towards filling cracks in asubstrate, e.g., a cement substrate. The cracks can be prefilled with apacking material, e.g., fiberglass rope that is coated or uncoated toprefill the crack. The packing material may include any compositematerial as described herein. If the packing material coated and/orsaturated with the VOC free low radiant flux UV curable material it iscured. The curing includes applying an energy source for about 2 minutesor less having wavelength in a range from about 360 nm to about 420 nmat a surface power density less than about 400 mW/cm² was applied tocure the material for about two minutes or less. Of course, other curingsurface power densities, curing times and/or additives may also beutilized as described herein. Next the crack is filled or partially withthe VOC free low radiant flux UV curable material it is cured asdescribed herein. This filling process and curing may be repeated. Thefinally surface can be leveled with a mechanical grinding means ifrequired.

One embodiment is directed towards a method of forming a chemicallyresistant non-permeable protective layer or coating. The chemicallyresistant coating may be resistant to acid of less than 0 pH, 1 pH, 2pH, 3 pH, 4 pH, 5 pH and higher. In addition, it is believed the coatingis also resistant to a higher alkalinity, e.g., 6 pH to about 14 pH.Therefore, the coating will withstand harsh and destructive elements,e.g., sea water, steam, non-diluted muriatic acid, and the like. Theprotective coating may be formed on the desired substrate or material byapplying a VOC free low radiant flux UV material to the material orsubstrate by any conventional technique, e.g., dipping, encapsulation,spray, paint brush, roller, combinations of the same or the like, topredetermined thickness. In a preferred embodiment, the thickness of thewet coating is in a range from about 2 mils to about 5 mils. Next, aradiation energy source having wavelength in a range from about 360 nmto about 420 nm at a surface power density less than about 40 mW/cm² wasapplied to cure the material for about two minutes or less. Of course,other curing surface power densities, curing times and/or additives mayalso be utilized as described herein. These steps are repeated until thedesired thickness is achieved. Optionally and/or alternatively, theenergy source may be pulsed, ramped non-linearly, ramped linearly orcombination as described herein.

One embodiment is directed towards a method of manufacturing apremanufactured panel for an aerospace vehicle or application, e.g.,decorative cabinets, walls, prefabricated panels and other materials. Inthis embodiment, a wood veneer is adhered to an aerospace substrate,e.g., honeycomb made of alloy, composite or combination of the same. Thewood veneer may have one or more surfaces treated with a fire retardant.In one embodiment the veneer is not treated with a fire retardant as theVOC free low radiant flux UV material is a fire retardant as discussedherein. The adhesive may include adhesives as known in the art, e.g., 3MHi-Strength 90 contact adhesive.

Optionally and/or alternatively, the veneer does not include a stain,but is a natural wood veneer, e.g., bird's eye maple. The methodincludes applying the VOC free low radiant flux UV material with apigment, e.g., stain as a liquid or powder, to the desired tone, to oneor more surfaces of the veneer. Optionally, the veneer may be entirelyencapsulated with the VOC free low radiant flux UV material. The staincolors or darkens the appearance of the veneer. Next, an ultraviolentenergy source in a range from about 360 nm to about 420 nm is applied tothe coating at a surface power density in range from about 3 mW/cm² toabout 400 mW/cm² to cure the applied material and in preferredembodiment is 40 mW/cm² or less. Additional layers and curing is doneuntil a desired thickness is reached. Pigments can also create atranslucent stain or toner and to create a specific finish appearanceand pattern on stain-grade wood and solid colored substrates. Thecoating serves at least four simultaneous purposes including a stain, afire-retardant, optionally an insulator, and a protective or a sealingcoating in one process step, thereby, reducing processing steps andoverall cost of forming the aircraft panel. The coating may beconfigured to any sheen gloss, semi-gloss, satin, flat, and egg shell.Optionally, the material in the initial coating, i.e., directly adjacentto the veneer, may be allowed to penetrate the veneer using a dwell timeof 30 seconds to about 60 minutes or more in an uncured state prior tocuring with energy source. This dwell time allows the material topenetrate into the veneer by absorbing into the body of the veneer,e.g., pores, cracks, micro-cracks. Optionally and/or alternatively, heatcan be applied to the material during the dwell time step or before thecoating step with a heat source, e.g., heat gun or other conventionalheating source. The heat allows moisture or VOC material in the veneerto be released.

One embodiment is directed towards a method of manufacturing hybridframe fabricated by initially forming a stack of fibrous layers or othercomposite material described herein in an annular pattern with a VOCfree low radiant flux UV material cured through a transparent mold withultraviolent energy source in a range from about 360 nm to about 420 nmat a surface power density in range from about 3 mW/cm² to about 40mW/cm² to cure. Other energies as described herein may be utilized.

One embodiment is directed towards forming an annular aircraft windowframe including forming a stack of fibrous layer or composite material(described herein) impregnated or soaked with a VOC free low radiantflux UV material as described herein in an annular pattern. Forming anannular metal trim conforming with said annular pattern, trapping saidtrim in a lower transparent mold having a lower mold channel, trappingsaid stacked layers atop said trim in said lower transparent moldchannel, and pressing an upper mold atop said stacked layers forcompression applying the ultraviolent energy source in a range fromabout 360 nm to about 420 nm at a surface power density as describedherein. Other energies as described herein may be utilized.

Optionally, and/or alternatively, the molds used in one or moreembodiments may include a transparent mold with or without transparentvacuum bags for forming composites. The molds may include an integratedenergy, e.g., embedded light emitting diodes, or any external energysource.

One embodiment is directed towards manufacturing a bathware by replacingthe porcelain over steel bathware or glazed bathware with the VOC freelow radiant flux UV material as described herein. The material is curedas described herein. As discussed herein several layers may be built upand cured. Optionally and/or alternatively, the bathware may be createdwith a mold injection bathware using the VOC free low radiant flux UVmaterial. The pigments and additional decorative components may be used.

One embodiment is directed towards bonding of two or more materials,e.g., securing the windings over the guide to the rod on a fishing rod,securing windings on a fishing fly, securing electrical windings onmotors, or any other process where the materials are desired to bebonded. In this embodiment, the materials to be bonded are coated orcovered with the VOC free low radiant flux UV material. Next, radiationfrom an energy source having wavelength in a range from about 360 nm toabout 420 nm at a surface power density less than about 40 mW/cm² isapplied to cure the material for about two minutes or less. Of course,other curing surface power densities, curing times and/or additives mayalso be utilized as described herein. These steps are repeated until canbe repeated until the desired thickness is achieved. In a preferredembodiment, surface preparation is done to ensure the surfaces of thematerials to be bonded are clean (free of waxes, greases, oils or othercontaminants) and dried. The applied material is done with a sufficientquantity to cover the materials to be bonded, however, when bondingdelicate materials, only small amounts of the VOC free low radiant fluxUV material is required to secure them together until either a thickerlayer or multiple layers are applied in a buildup process.

One embodiment is directed towards an insulator coating for electricalapplications. The VOC free low radiant flux UV material can be used tocover wires, e.g., bare wires, or other electrical components to anythickness as described herein by applying the material to a desiredthickness, curing the material and repeating. The cured material is anelectrical insulator.

One embodiment is directed towards an anti-tampering coating orjunction. This method may be useful for indicating a break in safetyprotocols requiring the physical security of an object within a storagecontainer or device. The VOC free low radiant flux UV material is usedto cover or create anti-tampering junction to any thickness as describedherein by applying the material to a desired thickness, curing thematerial and repeating. The cured material is now an anti-tamperingjunction, so one would know if the junction is open or broken. Ofcourse, pigments and other additives may be included as describedherein.

Reference will now be made in detail to embodiments of the invention,example of which is illustrated in the accompanying text.

FIG. 1A illustrates a top view of a damaged article according to anembodiment of the invention. FIG. 1B illustrates a cross sectional viewalong line A to A′ of the damaged article of FIG. 1A. FIG. 1Cillustrates a cross sectional view along line A to A′ of the repairedarticle of FIG. 1A. FIG. 1D illustrates a top down view of the repairedarticle.

Referring to FIGS. 1A-1D, the repair of an article 100 is generallydescribed. In FIG. 1A, the article 100 includes a VOC free low radiantflux UV cured material. In this embodiment, the VOC free low radiantflux UV cured material is described herein has damage 104 or a damagedregion 104. The VOC free low radiant flux UV cured material 102 is apreexisting coating on a substrate 106. The substrate 106 may includeany type of substrate, e.g., decorative material, cement, fiberglass,composite material, wood, veneer, metal, alloy, man-made fiber board,high density fiber board, medium density fiber board, low density fiberboard, cardboard, chipboard, particle board, Masonite, cement fiberboard, Mindy board and combinations of the same. Optionally, and/oralternatively, the substrate may include a honeycomb substrate made fromalloy, aluminum alloy, composite, fiberglass, carbon fiber,thermoplastic, wood, metal and combinations of the same. Optionally,and/or alternatively, the substrate may include a honeycomb substratemade from alloy, aluminum alloy, composite, fiberglass, carbon fiber,thermoplastic, wood, metal and combinations of the same with a woodveneer material adhered to the substrate.

In this embodiment, the cured coating was already present and formed byapplying a radiation energy source in a range from about 360 nm to about420 nm at a surface power density less than about 40 mW/cm² to the VOCfree low radiant flux UV cured material. In a preferred embodiment, theVOC free low radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing energies, surface powerdensities, and/or additives may also be utilized as described herein.

The cured coating 102 includes a cross-linked matrix and does not havedefinitive visible layers or a series of layers as would be present in aconventional urethane, VOC laden coating or non-radiation cured coating.The damaged region 104 is a three-dimensional damaged region and has adimension into the bulk surface of the coating 102, but does not impingeinto the substrate 106. That is, the substrate 106 is not damaged inthis embodiment only the cured coating 102 is damaged in region 104.

Referring now to FIG. 4 , the damaged article 100 is repaired withreference to method of repair 400. In this embodiment, the damagedarticle 100 is provided having a damaged region 104 (step 402). In step404, the damaged article 100 is cleaned with water, IPA, acetone orcombinations of the same. Preferably, the surface 102 of the damagedarticle 100 is cleaned with an isopropyl alcohol (IPA). Referring toFIG. 1B, the cleaned surface is prepared further (in Step 406) byremoving any rough surfaces, jagged edges and/or other damage to thedamaged article. In this embodiment in step 406 this may be done bymechanically removing, e.g., sanding, with an abrasive material, razorblade, knife, heat source and/or other techniques. Following step 406,the article is further cleaned like in step 404, e.g., with IPA. In thisembodiment, the substrate is not damaged, so step 410 is not required orperformed.

In step 412, the surface is now prepared for receiving UV composition byroughening the surface of the coated article to promote adhesion. In apreferred embodiment this may be done with an abrasive material, e.g.,sand paper. In a more preferred embodiment, the coating 102 is sandedwith liquid grit abrasive to roughen the surface and provide amechanical bond. This is also an optional step.

In step 414, a VOC free low radiant flux UV material is applied to thesubstrate by any conventional technique, e.g., spray, paint brush, dip,bath, roller, combinations of the same or the like, to a first thicknessto fill the damaged region 112. In a preferred embodiment, the thicknessof the wet coating is in a range from about 2 mils to about 5 mils orless and only partially fills the damaged coating. That is a conformalcoating is applied. Next, in step 416 a radiation energy source havingwavelength in a range from about 360 nm to about 420 nm at a surfacepower density less than about 40 mW/cm² was applied to cure the materialfor about two minutes or less. In a preferred embodiment, the VOC freelow radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing surface power densities,curing times and/or additives may also be utilized as described herein.Steps 414 and 416 are repeated until the desired thickness is achieved.In a preferred embodiment, steps 414 and 416 are repeated until theadded cured material has a thickness that is about 2 mils to about 4mils or greater than the surface of the preexisting cured material 102.Optionally and/or alternatively, the energy source may be pulsed, rampednon-linearly, ramped linearly or combination as described herein.

Next in step 418 the article is cleaned with water, IPA and/or acetone.In step 420 any excess material (2 mils or greater) is removed, e.g., byan abrasive material. In a preferred embodiment, the surfaces 108 and112 are planarized in step 420 by sanding and/or polishing with a seriesof abrasive materials, e.g., starting with a course abrasive and endingwith a fine abrasive. In a preferred embodiment the dry sanding includessanding with one or more of six different grits ranging from 600 grit to2000 grit. In a more preferred embodiment, the dry sanding componentsinclude a 600 grit material, 800 grit material, 1000 grit material, 1200grit material, 1500 grit material, and 2000 grit material. Next in step422 the article is cleaned with a material such as water, IPA and/oracetone.

Optionally, the article with the repaired coating is polished (step 424)with a liquid polish to any desired shine. Referring now to FIG. 1C,there is no visible discountinuity 110 between the repaired coating 112and the original coating 108. This is believed to be due to thecross-linked nature of the cured coating. By way of example, referringto FIG. 1D there is no visible, to a human eye, discountinuity betweenthe repaired coating 112 and the original material 108. This is indirect contrast to the related art. One problem with the conventionalcoatings is that any repair would show to the human eye a stop and startline in pattern, e.g., bullseye pattern, which is believed to be causedby the solvents present in at least one or more of the original coatingor repair coating.

It is believed the discontinuities are due to the solvents in theconventional material as they will show a margin line or discountinuityregion or other imperfection between the original material and therepaired material. It is also believed that this is caused by aninability to polish solvents. In contrast, in embodiments of thisinvention there is believed to be no, or virtually no, discountinuitypresent between the original coating and the repaired coating as fullpolishing is possible as there is approximately one hundred percentsolids in the cured repaired coating and the original coating as shownin FIG. 1C and FIG. 1D. This also means there would be no visiblediscontinuities to the human eye present between the repaired materialand the original material when looking at the repaired material from atop down view, angle view, side view or any combination view (FIGS. 1Cand 1D). As used herein the discontinuities can be characterized as astop and start line, margin line, or other visible imperfection betweenthe repaired region and the original region.

FIG. 2A illustrates a top view of a damaged article according to anotherembodiment of the invention. FIG. 2B illustrates a cross sectional viewalong line A to A′ of the damaged article of FIG. 2A. FIG. 2Cillustrates a cross sectional view along line A to A′ of the repairedarticle of FIG. 2A. FIG. 2D illustrates a top down view of the repairedarticle.

Referring to FIGS. 2A and 2B, the article 200 includes a cured VOC freelow radiant flux UV coating 202 that has damage or a damaged region 204.The article 200 includes a cured coating 202 on a substrate 206. Thesubstrate 206 may include any type of substrate, e.g., decorativematerial, cement, fiberglass, composite material, wood, veneer, metal,alloy, man-made fiber board, high density fiber board, medium densityfiber board, low density fiber board, cardboard, chipboard, particleboard, Masonite, cement fiber board, Mindy board and combinations of thesame. Optionally and/or alternatively, the substrate may include ahoneycomb substrate made from alloy, aluminum alloy, composite,fiberglass, carbon fiber, thermoplastic, wood, metal and combinations ofthe same with a wood veneer material adhered to the substrate.

In this embodiment, the cured coating was already present and formed byapplying a radiation energy source in a range from about 360 nm to about420 nm at a surface power density less than about 40 mW/cm² to the VOCfree low radiant flux UV cured material. In a preferred embodiment, theVOC free low radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing energies, surface powerdensities, and/or additives may also be utilized as described herein.

The cured coating 202 includes a cross-linked matrix or substantiallysolid material of about one hundred present solids and does not havedefinitive visible layers or a series of layers as would be present in aconventional urethane, VOC laden coating or non-radiation cured coating.

In this embodiment the damage 204 is a three-dimensional damage and hasa dimension into the bulk surface of the coating 202 and also damage onthe substrate 206. That is, the substrate 206 has damage in thisembodiment that needs to be repaired as well. In this embodiment, thesubstrate is a wood surface, e.g., a veneer wood surface.

Referring now to FIG. 4 , the damaged article 200 is repaired withreference to 400. In this embodiment, the damaged article 200 isprovided having a damaged region 204 (step 402). In step 404, thedamaged article 200 is cleaned with IPA, water, and/or acetone.Preferably, the surface 202 of the damaged article 200 is cleaned withIPA. Referring to FIG. 2B, the cleaned surface is prepared further (instep 406) to remove any rough surfaces, jagged edges and/or other damageto the damaged article. In this embodiment in step 406 this may be doneby a mechanical mechanism, e.g., sanding with an abrasive material,razor blade, knife, or done with a heat source and/or other techniques.Next, in step 408 the prepared article and/or surface is cleaned againas described with reference to step 404.

Next the substrate 206 is repaired in step 410. In this embodiment, awood filler or putty is used to repair the damage with an added stainmatching the original stain of the substrate 206. However, the repairmay include other techniques as known in the art that are substratedependent.

In step 412, the surface is now prepared for receiving the VOC free lowradiant flux UV cured material by roughening the surface of the coatedarticle to promote adhesion. In a preferred embodiment this may be donewith an abrasive material, e.g., sand paper. This step is optional.

In step 414, a VOC free low radiant flux UV material is applied to thesubstrate by any conventional technique, e.g., spray, paint brush, dip,bath, roller, combinations of the same or the like, to a first thicknessto fill the damaged region 204. In a preferred embodiment, the thicknessof the wet coating is in a range from about 2 mils to about 5 mils orless and only partially fills the damaged coating. That is a conformalcoating is applied. Next, in step 416 a radiation energy source havingwavelength in a range from about 360 nm to about 420 nm at a surfacepower density less than about 40 mW/cm² was applied to cure the materialfor about two minutes or less. In a preferred embodiment, the VOC freelow radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing surface power densities,curing times and/or additives may also be utilized as described herein.Steps 414 and 416 are repeated until the desired thickness is achieved.In a preferred embodiment, steps 414 and 416 are repeated until theadded cured material has a thickness that is about 2 mils to about 4mils or greater than the surface of the preexisting cured material 202.Optionally and/or alternatively, the energy source may be pulsed, rampednon-linearly, ramped linearly or combination as described herein.

Next in step 418 the article is cleaned with water, IPA and/or acetone.In step 420 any excess material (2 mils or greater) is removed, e.g., byan abrasive material. In a preferred embodiment, the surfaces 208 and212 are planarized in step 420 by sanding and/or polishing with a seriesof abrasive materials, e.g., starting with a course abrasive and endingwith a fine abrasive. In a preferred embodiment the dry sanding includessanding with one or more of six different grits ranging from 600 grit to2000 grit. In a more preferred embodiment, the dry sanding componentsinclude a 600 grit material, 800 grit material, 1000 grit material, 1200grit material, 1500 grit material, and 2000 grit material. Next in step422 the article is cleaned with a material such as water, IPA and/oracetone.

Optionally, the article with the repaired coating is polished (step 424)with a liquid polish to any desired shine. Referring now to FIG. 2C,there is no visible discountinuity 211 between the repaired coating 208and the original coating 208. This is believed to be due to thecross-linked nature of the cured coating. By way of example, referringto FIG. 2D there is no visible to a human eye discountinuity between therepaired coating 212 and the original material 208. This is in directcontrast to the related art. One problem with the conventional coatingsis that any repair would show to the human eye a stop and start line inpattern, e.g., bullseye pattern, which is believed to be caused by thesolvents present in at least one or more of the original coating orrepair coating.

It is believed the discontinuities are due to the solvents in theconventional material as they will show a margin line or discountinuityregion or other imperfection between the original material and therepaired material. It is believed that this is due to one's inability topolish solvents. In contrast, in embodiments of this invention there isno, or virtually no, discountinuity present between the original coatingand the repaired coating as full polishing is possible as there isapproximately one hundred percent solids in the cured repaired coatingand the original coating as shown in FIG. 2C and FIG. 2D. This alsomeans there are no visible discontinuities to the human eye presentbetween the repaired material and the original material when looking atthe repaired material from a top down view, angle view, side view or anycombination view (FIGS. 2C and 2D). As used herein the discontinuitiescan be characterized as a stop and start line, margin line, or othervisible imperfection between the repaired region and the originalregion.

FIG. 3A illustrates a top view of a damaged article accordingly articleaccording to another embodiment of the invention. FIG. 3B illustrates across sectional view along line A to A′ of the damaged article of FIG.3A. FIG. 3C illustrates a cross sectional view along line A to A′ of therepaired article of FIG. 3A. FIG. 3D illustrates a top down view of therepaired article.

Referring to FIGS. 3A and 3B, the article 300 includes a cured VOC freelow radiant flux UV coating 302 that has damage 304 or a damaged region304. The article 300 includes a cured coating 302 on a substrate 306.The substrate 306 may include any type of substrate, e.g., decorativematerial, cement, fiberglass, composite material, wood, veneer, metal,alloy, man-made fiber board, high density fiber board, medium densityfiber board, low density fiber board, cardboard, chipboard, particleboard, Masonite, cement fiber board, Mindy board and combinations of thesame. Optionally and/or alternatively, the substrate may include ahoneycomb substrate made from alloy, aluminum alloy, composite,fiberglass, carbon fiber, thermoplastic, wood, metal and combinations ofthe same with a wood veneer material adhered to the substrate.

In this embodiment, the cured coating was already present and formed byapplying a radiation energy source in a range from about 360 nm to about420 nm at a surface power density less than about 40 mW/cm² to the VOCfree low radiant flux UV cured material. In a preferred embodiment, theVOC free low radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing energies, surface powerdensities, and/or additives may also be utilized as described herein.

Optionally and/or alternatively, an additional substrate 306 waspresent. The additional substrate 306 can be any substrate as describedherein. In this embodiment, the substrate 304 includes a honeycombstructural material and the substrate 306 is a decorative material,e.g., wood veneer, adhered to a surface of the substrate 304. The curedcoating 302 includes does not have definitive visible layers or a seriesof layers as would be present in a conventional urethane, VOC ladencoating or non-radiation cured coating.

The damage 304 is a three-dimensional damage and has a dimension intothe bulk surface of the coating 302 and also no damage on the substrate306. That is, the substrate 306 or 304 in this embodiment is not damagedin this embodiment.

Referring now to FIG. 4 , the damaged article 300 is repaired withreference to 400. In this embodiment, the damaged article 300 isprovided having a damaged region 304 (step 402). In step 404, thedamaged article 300 is cleaned as described herein. Preferably, thesurface 302 of the damaged article 308 is cleaned with IPA. Referring toFIG. 3B, the cleaned surface is prepared further (in step 406) to removeany rough surfaces, jagged edges and/or other damage to the damagedarticle. In this embodiment in step 406 maybe done with a mechanicalmechanism, e.g., sanding with an abrasive material, razor blade, knife,or heat source and/or other treatment techniques. In step 408 theprepared article and/or surface is cleaned as described herein, e.g.,with IPA.

In this embodiment, there is no damage to the substrate 306 or 308.However, if there was damage to the substrate 306 or 308 it could berepaired in optional step 410.

In step 412, the surface is now prepared for receiving the VOC free lowradiant flux UV cured material by roughening the surface of the coatedarticle to promote adhesion. In a preferred embodiment this may be donewith an abrasive material, e.g., sand paper. In a more preferredembodiment, the coating 302 is sanded with liquid grit abrasive. Thisstep is also optional.

In step 414, a VOC free low radiant flux UV material is applied to thesubstrate by any conventional technique, e.g., spray, paint brush, dip,bath, roller, combinations of the same or the like, to a first thicknessto fill the damaged region 304. In a preferred embodiment, the thicknessof the wet coating is in a range from about 2 mils to about 5 mils orless and only partially fills the damaged coating. That is a conformalcoating is applied. Next, in step 416 a radiation energy source havingwavelength in a range from about 360 nm to about 420 nm at a surfacepower density less than about 40 mW/cm² was applied cure the materialfor about two minutes or less. In a preferred embodiment, the VOC freelow radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing surface power densities,curing times and/or additives may also be utilized as described herein.Steps 414 and 416 are repeated until the desired thickness is achieved.In a preferred embodiment, steps 414 and 416 are repeated until theadded cured material has a thickness that is about 2 mils to about 4mils or greater than the surface of the preexisting cured material 302.Optionally and/or alternatively, the energy source may be pulsed, rampednon-linearly, ramped linearly or combination as described herein.

Next in step 418 the article is cleaned with water, IPA and/or acetone.In step 420 any excess material (2 mils or greater) is removed, e.g., byan abrasive material. In a preferred embodiment, the surfaces 309 and312 are planarized in step 420 by sanding and/or polishing with a seriesof abrasive materials, e.g., starting with a course abrasive and endingwith a fine abrasive. In a preferred embodiment the dry sanding includessanding with one or more of six different grits ranging from 600 grit to2000 grit. In a more preferred embodiment, the dry sanding componentsinclude a 600 grit material, 800 grit material, 1000 grit material, 1200grit material, 1500 grit material, and 2000 grit material. Next in step422 the article is cleaned with a material such as water, IPA and/oracetone.

Optionally, the article with the repaired coating is polished (step 424)with a liquid polish to any desired shine. Referring now to FIG. 3C,there is no visible discountinuity 311 between the repaired coating 312and the original coating 308. This is believed to be due to thecross-linked nature of the cured coating. By way of example, referringto FIG. 3D there is no visible to a human eye discountinuity between therepaired coating 312 and the original material 308 as shown 316. This isin direct contrast to the related art. One problem with the conventionalcoatings is that any repair would show to the human eye a stop and startline in pattern, e.g., bullseye pattern, which is believed to be causedby the solvents present in at least one or more of the original coatingor repair coating.

It is believed the discontinuities are due to the solvents in theconventional material as they will show a margin line or discountinuityregion or other imperfection between the original material and therepaired material. It is believed that this is due to one's inability topolish solvents. In contrast, in embodiments of this invention there isno or virtually no discountinuity present between the original coatingand the repaired coating as full polishing is possible as there isapproximately one hundred percent solids in the cured repaired coatingand the original coating as shown in FIG. 3C and FIG. 3D. This alsomeans there are no visible discontinuities to the human eye presentbetween the repaired material and the original material when looking atthe repaired material from a top down view, angle view, side view or anycombination view (FIGS. 3C and 3D). As used herein the discontinuitiescan be characterized as a stop and start line, margin line, or othervisible imperfection between the repaired region and the originalregion.

One embodiment is directed towards repairing a damaged region, e.g.,structural breaks, punctures in composite bathware fiberglass, acrylicproducts and the like. In this embodiment, one or more steps 402, 404,406, 408, 410, and 412 is conducted. Next, a composite material asdescribed herein is used by applying the VOC free low radiant flux UVmaterial to the composite material by soaking or impregnating thematerial. The composite impregnated material may be applied to releasematerial (preferably transparent to UV radiation). The impregnatedmaterial is cured with an energy source as described herein. The curedrigid composite material now a patch material is trimmed and sized tofit in cavity of the damaged material. The patch material is coveredwith the VOC free low radiant flux UV material to cover the cavity orresides within a portion of the cavity and cured with an energy sourcedescribed herein. A skim coating of pigmented VOC free UV CurableComposition paste matching the outer surface can be used and appliedwith a skim coat until level with surface. This is cured with an energysource as described herein.

FIG. 5A illustrates a method of forming a composite apparatus accordingto an embodiment of the invention.

Referring to FIG. 5A, the composite article is formed with reference toa method 500. The method 500 includes a providing a composite mold (step502) and applying a mold release material (step 504) to at least aportion of the mold. The mold release material is a material configuredto prevent the VOC free low radiant flux UV material from sticking tothe mold when forming a composite. In a preferred embodiment, the moldrelease agent is energy transparent allowing an energy source havingwavelength in a range from about 360 nm to about 420 nm to pass throughthe mold release agent with minimal interference.

Applying the mold release step 504 is optional as it is utilized toassist the release the formed material from the mold. The mold releaseagent is known in the art and in preferred embodiment, includes anaqueous mixture of water and acetone such as Rain-X® 2-N-1 GlassCleaner+Rain Repellent.

In step 506 a composite material is arranged on a surface of the mold.The composite material may include one or more layers. The orientationof the layers may change as relative to each other. For example, theorientation of the first layer may be different, e.g., angled,orthogonal, to the orientation of the second layer. The compositematerial may include a semi-synthetic fiber, a cellulose fiber, afiberglass fiber, a carbon fiber, synthetic fiber, a metallic fiber, asilicon carbide fiber, a mineral fiber, polymer fiber, a microfiber andcombinations of the same. In step 508, the VOC free low radiant flux UVmaterial is applied to the composite to substantially saturate or soakthe material. In step 506, the composite material may in of asemi-synthetic fiber, a cellulose fiber, a fiberglass fiber, a carbonfiber, synthetic fiber, a metallic fiber, a silicon carbide fiber, amineral fiber, polymer fiber and a microfiber. Optionally and/oralliteratively, the composite material and the VOC free low radiant fluxUV material can be applied in a single step, e.g., a pre-impregnatedmaterial described herein.

In step 510 a radiation energy source having wavelength in a range fromabout 360 nm to about 420 nm at a surface power density less than about40 mW/cm² was applied to cure the material for about two minutes orless. In a preferred embodiment, the VOC free low radiant flux UV curedmaterial includes an acrylate monomers/oligomers, a thiolmonomers/oligomers, a photo initiator, and a radical inhibitor. Ofcourse, other curing surface power densities, curing times and/oradditives may also be utilized as described herein. Steps 506, 508 and510 are repeated until the desired thickness of composite material isachieved. Optionally and/or alternatively, the energy source may bepulsed, ramped non-linearly, ramped linearly or combination as describedherein. Optional additional components may include glass/silica fillersand pigments to the material.

Optionally and/or alternatively, the energy source may be appliedsimultaneously to a first and second opposite side of the saturatedcomposite material with a UV transparent mold. A UV transparent mold isconfigured to allow an energy source having wavelength in a range fromabout 360 nm to about 420 nm to pass through the mold. The mold may bemade from a thermoplastic material or may be glass.

Optionally and/or alternatively, the mold includes a vacuum bag andvacuum source that uses a negative pressure to hold the coated compositeprior to curing in place until it cures. The vacuum bagging also assistswith saturating or soaking the VOC free low radiant flux UV materialinto the composite material. In this embodiment, the vacuum bag would beUV transparent bag configured to allow an energy source havingwavelength in a range from about 360 nm to about 420 nm to pass throughthe bag. Optionally and/or alternatively, the mold includes an autoclavemold.

In one embodiment, the mold may be configured to form a part or anygeometric shape. Some typical examples of a mold shapes include abathware mold, such as a tube, sink, shower stall, a boat haul mold, aswimming pool mold, a spa mold, an aircraft component mold, a windmillcomponent mold, such as a windmill blade mold, automotive part mold, anautomotive fender, an automotive body mold, and a part mold.

In step 512 the cured composite material is released from the mold.

In one embodiment, using the steps 502,504, 506, 508, 510 and 512 one ormore of a boat haul, airfoil, part or other device can be fabricated.

FIG. 6 illustrates a method of resurfacing a swimming pool or spaaccording to an embodiment of the invention.

A pool or spa resurfacing or remolding method is generally describedwith reference to method 600. The main types of in-ground swimming poolsbase material include a fiberglass material, a shotcrete material, aconcrete material, a gunite material and a vinyl liner material.

Gunite is a mixture of sand and concrete that can be poured into anyshape, which makes them popular. Typically, after the pool is formedwith the base material and plaster is shot and troweled to finish thepool when the base material is shotcrete, concrete, and/or gunite. Othertypes of material including pebbles and quartz plaster may be used tofinish the pool. Plaster is least effective when it comes to life of thepool lasting about 5 years, pebbles last about 10 years and quartz andplaster lasts about 7 years. The coating of the pools needs to bereplaced as plaster has surface irregularities overtime, which may takeon a beige hue caused by chemical etching. That is, the chemical etchingcan be caused by low pH or alkalinity; an acidic condition in the pool.It may begin within the plaster, from the original mix on application,or etching may start from the gunite side of the plaster and work itselffrom the outside in. Plaster etching can also be the result ofaggressive or improper acid washing.

One embodiment of the invention is directed towards a method of usingthe VOC free low radiant flux UV curable material to coat, resurface,surface and/or repair an existing pool base material including one ormore of a fiberglass material, a shotcrete material, a concretematerial, a gunite material and a vinyl liner material. Referring now toFIG. 6 , the method 600 includes providing or forming an existing poolbase material (step 602). This may include draining an existing pool orforming an existing pool out of one more of the existing pool basematerials. The existing pool base materials now need to be prepared instep 604. The preparing step 604 is dependent on whether the existingpool base material is being resurfaced or new and type of the existingpool base material.

When resurfacing a plaster coated existing pool base material, step 604includes removing at least a portion of the old plaster and/or colorcoat. The removing may be done with conventional equipment as known inthe art, sander, disc grinder, e.g., 30 grit disc, sand blaster and/orother tool. Next the surface having the removed plaster is washed and/orwashed, e.g., pressured washed, with a cleaning solution, e.g., acidiccleaning solution, and allowed to dry.

When resurfacing a fiberglass or vinyl existing pool material without atop plaster coating, step 604 includes cleaning the surface of theexisting pool base material fiber. This cleaning and preparation may bedone with water, a cleaning solution, and/or an abrasive material.

Optionally, in step 606 the cleaned surface, from step 604, is leveledwith a leveling agent, e.g., a skim coating, over defects or unlevelsurfaces to level and/or repaired to correct any defects in either theexisting pool material or existing plaster. The leveling agent is knownin the art.

Optionally, the cleaned surface from step 604 material is sealed with asealant material (step 608) as known in the art and/or an adhesionpromoter is utilized. In preferred embodiment, the sealant material isthe UV VOC free low radiant flux UV material described herein applied ina thin layer and allowed to cure in the ambient sunlight and/or withenergy sources described herein. In one embodiment, the adhesionpromoter is configured to promote adhesion of the UV VOC free lowradiant flux UV material to the cleaned surface and/or the sealedsurface.

Optionally, the surface from steps 604, 606 or 608 is coated with aprimer, colored primer, and/or other colorant. This step 610 enables oneto change the color of an existing surface. However, this step 610 isoptional and the coloring can be done a pigmented UV VOC free lowradiant flux UV material.

Next in step 612 a UV the VOC free low radiant flux UV material isapplied to the surface from step 604, 606, 608, or 610 to a desiredthickness. Prior to applying the UV the VOC free low radiant flux UVmaterial to the surface, pool, partial pool and/or entire pool iscovered with a UV protective barrier. The UV protective barrier may be atent, mechanical cover, existing pool cover, that is covered to block UVradiation to prevent curing. This material may be applied with anyconventional techniques, e.g., roller, paintbrush, spray or othertechniques.

In one embodiment, the composite material may include one or more of asemi-synthetic fiber, a cellulose fiber, a fiberglass fiber, a carbonfiber, a synthetic fiber, a metallic fiber, a silicon carbide fiber, amineral fiber, a polymer fiber, a microfiber and combinations of thesame or the like. The composite material may be configured as patch,sheet, cloth, woven, non-woven or other orientation or configurations.

Next, in step 614 a radiation energy source having wavelength in a rangefrom about 360 nm to about 420 nm at a surface power density less thanabout 40 mW/cm² is applied to cure the material for about two minutes orless. Optionally and/or alternatively, the radiation energy may beambient sunlight. In a preferred embodiment, the VOC free low radiantflux UV cured material includes an acrylate monomers/oligomers, a thiolmonomers/oligomers, a photo initiator, and a radical inhibitor. Ofcourse, other curing surface power densities, curing times and/oradditives may also be utilized as described herein. Optionally and/oralternatively, the radiation energy may be ambient sunlight. Steps 612and 614 are repeated until the desired thickness is achieved.

Optionally and/or alternatively, in step 616 a decorative material isapplied to a non-cured VOC free low radiant flux UV cured material priorto coating or after coating in this step. The decorative material mayinclude glitter, metallic flakes, thermoplastic flakes, beads, glassbeads, thermoplastic beads, decals, stickers, organic pigmentedmaterials, synthetic pigmented materials of any color or any combinationof the foregoing. The decal and/or sticks can be custom configured witha logo or any type of graphic. Optionally and/or alternatively, the UVcurable composition further includes a pigment configured to color thesurface of the coating, e.g., up to 5% by volume to create a transparenttone to a solid colored coating; any color may be achieved, e.g., red,blue, green and any combination. In a preferred embodiment, the surfaceis white or blue. The coating will withstand harsh and destructiveelements, e.g., sea water, steam, non-diluted muriatic acid, and thelike. Optionally and/or alternatively, step 618 includes applying afinal clear coat and curing the same to cover the decorative coating.This step 618 is done as similarly described with regard to steps 612and 614.

FIG. 7 illustrates a method of repairing a pipe or pipeline according toan embodiment of the invention.

Referring to FIG. 7 , the method 700 includes in providing an existingpipe or pipeline (step 702). The pipe or pipeline may be constructedfrom cement material, e.g., a sewer, fiberglass, or thermoplastic orother material. If treating the external surface of the pipe this stepmay include excavating material around the pipe to provide access to theregion or portion of the pipe to be repaired. Optionally and/oralternatively, this method can be used as a reinforcement mechanism toreinforce pipe or pipeline adding strength.

In step 704 the existing pipe or pipeline surface is prepared. This stepmay vary somewhat depending on the size of the pipe and whether theinternal or external portion of the pipe is being prepared. Whentreating an external portion of the pipe or pipeline the exposed surfaceof the pipe is clean and/or abraded to remove existing coatings ordebris. The cleaning may be accomplished with mechanical mechanismsincluding sanders, grinders, particle blasting and other techniquesknown in the art. The surface is now cleaned with water, IPA, acetoneand combinations of the same to remove dust and other containments. Nextthe surface is allowed to dry naturally or with the aid of heater. Iftreating an internal portion of the pipe or pipeline the exposed surfaceof the pipe is cleaned and/or abraded to remove existing coatings ordebris. The cleaning may be accomplished with mechanical mechanismsincluding sanders, grinders, particle blasting and other techniquesknown in the art. The surface is now cleaned with water, IPA, acetoneand combinations of the same to remove dust and other containments. In apreferred embodiment, a texture, e.g., a roughened surface, is appliedto the pipe or pipeline to promote mechanical adhesion of the coating tobe applied.

Optionally step 706 is performed if the pipe or pipeline has damagedregions they can be fixed by patching as described herein and/or filingvoids as described herein with reference to FIGS. 2A to 4 and relatedtext.

Optionally in step 708 depending on the pipe or pipeline material to betreated a sealant and/or adhesion coating can be applied. The cleanedsurface of the pipe or pipeline is sealed with a sealant material (step708) as known in the art and/or an adhesion promoter is utilized asknown in the art. In preferred embodiment, the sealant material and/oradhesion promoter is the UV VOC free low radiant flux UV materialdescribed herein applied in a thin layer (2 mils or less) and allowed tocure in the ambient sunlight and/or with energy sources describedherein.

In step 710 the existing pipe or pipeline surface is treated by applyingthe UV VOC free low radiant flux UV material to the pipe. This step mayvary somewhat depending on the size of the pipe and whether the internalor external portion of the pipe is being prepared. When treating anexternal portion of the pipe or pipeline the UV VOC free low radiantflux UV material to the pipe can be applied by pre-impregnated (pre-peg)roll or patch of composite material (described herein) that is saturatedwith a UV VOC free low radiant flux UV material. In a preferredembodiment, the roll is in a range from about 2 ft. to about 20 ft ormore in width and has a diameter from about 1 foot or greater. The roleis pre-peg of composite material saturated with the UV VOC free lowradiant flux UV material and packed in a UV radiation blocking material,e.g., foil or other UV blocking material.

In step 710 the prep-preg material can include one or more layers ofcomposite material. The orientation of the layers may change as relativeto each other. For example, the orientation of the first layer may bedifferent, e.g., angled, orthogonal, to the orientation of the secondlayer. The composite material may include one or more a semi-syntheticfiber, a cellulose fiber, a fiberglass fiber, a carbon fiber, syntheticfiber, a metallic fiber, a silicon carbide fiber, a mineral fiber,polymer fiber, a microfiber and combinations of the same. Pre-pegsubstantially saturated or soaked with the UV VOC free low radiant fluxUV material. Optionally and/or alternatively, the coating may be onlythe UV VOC free low radiant flux UV material without a compositematerial, the UV VOC free low radiant flux UV material arranged over acomposite material that is not a pre-peg material or any combination.

In this embodiment, the pre-peg material is wrapped in an overlappingspiral fashion such that at least a portion of the pre-peg materialoverlaps each other, e.g., a portion of the pre-peg material overlapsanother portion of the pre-peg material in a spiral fashion. Thiswrapping is applied under a UV shade, tent or other UV blocker toprevent curing.

Next, in step 714 a radiation energy source having wavelength in a rangefrom about 360 nm to about 420 nm at a surface power density less thanabout 500 mW/cm² is applied to cure the material for about two minutesor less. In a preferred embodiment, the energy surface power density isless than about 40 mW/cm². Optionally and/or alternatively, theradiation energy may be ambient sunlight. In a preferred embodiment, theVOC free low radiant flux UV cured material includes an acrylatemonomers/oligomers, a thiol monomers/oligomers, a photo initiator, and aradical inhibitor. Of course, other curing surface power densities,curing times and/or additives may also be utilized as described herein.Steps 710 and 714 can also be repeated until the desired thickness isachieved.

In step 710 the existing pipe or pipeline surface is treated with byapplying the UV VOC free low radiant flux UV material to internalsurface of the pipe. This can be done by apply with any conventionaltechnique and/or a pre-impregnated (pre-peg) roll or patch of compositematerial (described herein) that is saturated with a UV VOC free lowradiant flux UV material. The roll pre-peg material can be in a sockconfiguration having a desired length and diameter. The pre-peg isapplied with an airbladder that expands and presses the outside diameterof sock on the internal diameter of the pipe or mechanically applied.

Next in step 714 a radiation energy source having wavelength in a rangefrom about 360 nm to about 420 nm at a surface power density less thanabout 500 mW/cm² is applied to cure the material for about two minutesor less. In a preferred embodiment, the energy surface power density isless than about 40 mW/cm². Of course, other curing surface powerdensities, curing times and/or additives may also be utilized asdescribed herein. Steps 710 and 714 can also be repeated until thedesired thickness is achieved.

EXAMPLES

Without intending to limit the scope of the invention, the followingexamples illustrate how various embodiments of the invention may be madeand/or used.

Example 1

This Example 1 illustrates the manufacture of three separate testarticles prepared for a twelve (12) second vertical flammability test.Each of the test articles was coated with BlueSky Armor™ 1027 Clear TopCoat out of Boulder, Colorado, including acrylate monomers/oligomers,thiol monomers/oligomers, photo initiators and radical inhibitors. Eachof the test articles had a substrate that was 3 inches by 12 inches. Thesubstrate was an aluminum honeycomb panel from Teklam Corporation: P.O.6520, P/N AA207-33-500A, Job No. T017654-1-1 (Mfg Date 9/26/12). Abirdseye maple veneer from Goodrich Corporation: Kig No.PIR-111116-1-11/16/2011, having a back and core fire treated was adheredto a first surface of each of the test articles using a 3M: Hi-Strength90 contact adhesive and left to dry for about 10 hours.

The veneered surface was treated with a first coat of the material witha conventional high-volume, low-pressure (HVLP) automotive spray gun ata distance of about six to twelve inches to form a medium wet coat ofabout 2 mils to about 4 mils thickness. Next, the surface was cured witha low intensity UV light source having a wavelength in a range fromabout 360 nm to about 405 nm at a surface power density at 3 mW/cm² forabout seconds to about 60 seconds. After the curing the first coatingwas completely cured and tack free. Tack free was tested by checking thecured coating every 15 seconds or less by touching the surface of thecoating. If the sample was marred in any way the material was consideredtacky. This coating and curing step was repeated seven additional timesto form a cured coating having a thickness of about 20 mils to 25 mils.The total cure time for the coating was about 210 seconds. Each of thethree coated veneer articles were tested by Skandia Laborites under theVertical Flame Test codified at 14 C.F.R. Part 25.853 (a) Amdt AppendixF Part I (a)(1)(ii). The results of the test are shown in Table 1.

TABLE 1 Scandia Test Results for 12 Second Vertical Burn: FlameApplication Flame Time Burn Length Drip Flame Time Set (seconds)(seconds) (inches) (seconds) 1 12 0.0 0.2 0.0 2 12 0.0 0.2 0.0 3 12 0.00.3 0.0 Average: 0.0 0.2 0.0

As shown in Table 1, each of the three articles passed the 12 secondVertical Flammability Test. Accordingly, each of the tested articles isfire resistant, since each passed the 12 second Vertical FlammabilityTest. In addition, the test proves that each of the tested articles hada flame time of 0 seconds and drip flame time of 0 seconds. Accordingly,it was determined that the applied coating has a dual purpose of asingle stage coating, which is a clear coat, and fire retardant orresistant coating in one step. Moreover, this article can be used in theaerospace industry as it passed the 12 second Vertical FlammabilityTest.

Example 2

This Example 2 illustrates the manufacture and testing of three testarticles for a 60 second vertical flammability test and its results. Thetest article was coated with BlueSky Armor™ 1027 Clear Top Coat out ofBoulder, Colorado, including acrylate monomers/oligomers, thiolmonomers/oligomers, photo initiators and radical inhibitors. Each of thethree test articles was made with a separate substrate that was 3 inchesby 12 inches. Each of the substrates was an aluminum honeycomb panelfrom Teklam Corporation: P.O. 6520, P/N AA207-33-500A, Job No.T017654-1-1 (Mfg Date 9/26/12). A birdseye maple veneer from GoodrichCorporation: Log No. PIR-111116-1-11/16/2011, back and core fire treatedwas adhered to a first surface of the substrate using substrate adhesivefrom 3M: Hi-Strength 90 contact adhesive, and left to dry for about 10hours.

The veneered surface was treated with a first coat of the compositionwith a conventional HVLP automotive spray gun at a distance of about sixinches to form a medium wet coat of about 2 mils to about 4 mils. Next,the surface was cured with a low intensity UV light source having awavelength in the range from about 360 nm to about 405 nm at a surfacepower density of 3 mW/cm² for about 30 seconds to about 60 seconds.After curing the coating was completely cured and tack free. Tack freewas tested as described herein. This coating and curing step wasrepeated seven additional times to form a thickness of about 20 mils to25 mils. The total cure time for the coating was about 210 seconds. Thiscoated veneer article was tested by Skandia Laborites under the codified60 second Vertical Flame Test codified at 14 C.F.R. Part 25.853 (a) Amdt25-116 Appendix F Part I (a)(1)(ii). The results of the test are shownin Table 2.

TABLE 2 Scandia Test Results for 60 Second Vertical Burn: FlameApplication Flame Time Burn Length Drip Flame Time Set (seconds)(seconds) (inches) (seconds) 1 60 0.0 1.2 0.0 2 60 0.0 1.6 0.0 3 60 0.01.5 0.0 Average: 0.0 1.4 0.0

Each of the test articles passed the 60 second Vertical FlammabilityTest. Accordingly, each of the test articles is fire resistant as itpassed the test. In addition, the test shows each of the articles had aflame time of 0 seconds and drip flame time of 0 seconds. Therefore, theapplied coating had a dual purpose single stage coating; the dualpurpose was a clear coat and fire retardant or resistant coating. Thisarticle can be used in the aerospace industry as it passed the 60 secondVertical Flammability Test.

Example 3

This Example 3 illustrates the manufacture of a test article fortreatment with acid to show durability, chemical resistant andpermeability of the coating. In this Example, a USG Durock® Brand CementBoard about ½ inch thick board cut to about 3 inches wide by 10 incheslong was used. A copper-plated zinc United States penny was arranged onone surface of the cement board and the cement board was treated on allsides, front, back, and sides, with a first coat of BlueSky Armor™ 1027Clear Top Coat out of Boulder, Colorado including acrylatemonomers/oligomers, thiol monomers/oligomers, photo initiators andradical inhibitors. The composition was applied with a brush to athickness of about 8 mils or more. Next, the surface was cured with alow intensity UV light source having a wavelength in the range fromabout 360 nm to about 405 nm at a surface power density of 3 mW/cm² forabout 60 seconds. After curing the coating was completely cured and tackfree in an oxygen environment. This coating and curing step was repeatedtwo additional times to increase the thickness of the coating to about30 mils. The final test article included a completely coated cementsubstrate with a copper-plated zinc coin adhered to the substrate andalso coated.

The test article was submerged in muriatic acid from Klean Strip GreenMuriatic Acid from W.M. Barr in Memphis, TN, for about five days. Thetest article was removed and cleaned with water and it showed zero signsof wear due to the muriatic acid: no deterioration, degradation,corrosion, staining, or color change was visible. In addition, a cementboard described herein was also submerged without a coating and it wasdestroyed completely, almost immediately; the only item left was awebbing material, all cement was gone or deteriorated. This Exampleconfirms that cured coating is non-permeable and chemically resistant toa pH of less than 1.

Example 4

In this Example the characteristics and properties of BlueSky Armor™1007 Clear Top Coat, BlueSky Armor™, 1027 Clear Top Coat, BlueSky Armor™1047 Clear Knife Grade Filler, and BlueSky Armor™ 1057 Laminating Resinfrom MSI Coatings, Inc. out of Boulder, Colorado, were quantified.

More specifically, an acrylate conversion versus time was determinedwith a Nicolet FTIR spectrometer to collect real time conversion data ofMSI products. Conversion was determined using the acrylate functionalgroup absorbance peak at about 6200 cm⁻¹. A first energy source withthat was a 120 Watt LED light having a wavelength of 385-410 nmmanufactured by ADJ UV Cob Cannon was used as the energy source andcuring each of the materials at a low radiant flux at the surface of thematerial of 5 mW/cm², 10 mW/cm², and 20 mW/cm². A second energy sourcehaving a 30 Watt LED light having wavelength in a range from 385-410 nmLED light manufactured by ADJ Eco UV Bar 50 IR was used as the energysource for curing the material at a low radiant flux at the surface of2.5 mW/cm². In this Example 4 four separate testing slides were made foreach material. The light intensity in this Example was measured with anInternational Light model IL1400 with detector model XRL 140A.

More specifically, BlueSky Armor™ 1007 Clear Top Coat uncured materialwas placed on Corning 2947-75X25 Soda Lime Glass Plain Microscope Slidethat was 75 mm Length×25 mm Width×0.90-1.10 mm thick. The uncuredmaterial was drawn down across the slide with an AccuDyne #100wire-wound metering rod, so that the slide was completely and uniformlycovered with the wet material to a thickness of about 0.25 mm. Next, thewet slide was placed in the Nicolet FTIR spectrometer and cured at a lowradiant flux of 2.5 mW/cm² and real time conversion data was collectedas shown in FIG. 8 and Table 1. This process was repeated with BlueSkyArmor™ 1007 Clear Top Coat and the wet slide was placed in the NicoletFTIR spectrometer and cured at a low radiant flux of 5 mW/cm² and realtime conversion data was collected as shown in FIG. 8 and Table 1. Thisprocess was repeated with BlueSky Armor™ 1007 Clear Top Coat and the wetslide was placed in the Nicolet FTIR spectrometer and cured at a lowradiant flux of 10 mW/cm² and real time conversion data was collected asshown in FIG. 8 and Table 1. This process was repeated with BlueSkyArmor™ 1007 Clear Top Coat and the wet slide was placed in the NicoletFTIR spectrometer and cured at a low radiant flux of 20 mW/cm² and realtime conversion data was collected as shown in FIG. 8 and Table 1.

BlueSky Armor™ 1027 Clear Top Coat uncured material was placed onCorning 2947-75X25 Soda Lime Glass Plain Microscope Slide that was 75 mmLength×25 mm Width×0.90-1.10 mm thick. The uncured material was drawndown across the slide with an AccuDyne #100 wire-wound metering rod, sothat the slide was completely and uniformly covered with the wetmaterial to a thickness of about 0.25 mm. Next, the wet slide was placedin the Nicolet FTIR spectrometer and cured at a low radiant flux of 2.5mW/cm² and real time conversion data was collected as shown in FIG. 9and Table 1. This process was repeated with BlueSky Armor™ 1027 ClearTop Coat and the wet slide was placed in the Nicolet FTIR spectrometerand cured at a low radiant flux of 5 mW/cm² and real time conversiondata was collected as shown in FIG. 9 and Table 1. This process wasrepeated with BlueSky Armor™ 1027 Clear Top Coat and the wet slide wasplaced in the Nicolet FTIR spectrometer and cured at a low radiant fluxof 10 mW/cm² and real time conversion data was collected as shown inFIG. 9 and Table 1. This process was repeated with BlueSky Armor™ 1027Clear Top Coat and the wet slide was placed in the Nicolet FTIRspectrometer and cured at a low radiant flux of 20 mW/cm² and real timeconversion data was collected as shown in FIG. 9 and Table 1.

BlueSky Armor™ 1047 Clear Top Coat uncured material was placed onCorning 2947-75X25 Soda Lime Glass Plain Microscope Slide that was 75 mmLength×25 mm Width×0.90-1.10 mm thick. The uncured material was drawndown across the slide with an AccuDyne #100 wire-wound metering rod, sothat the slide was completely and uniformly covered with the wetmaterial to a thickness of about 0.25 mm. Next, the wet slide was placedin the Nicolet FTIR spectrometer and cured at a low radiant flux of 2.5mW/cm² and real time conversion data was collected as shown in FIG. 10and Table 1. This process was repeated with BlueSky Armor™ 1047 ClearTop Coat and the wet slide was placed in the Nicolet FTIR spectrometerand cured at a low radiant flux of 5 mW/cm² and real time conversiondata was collected as shown in FIG. 10 and Table 1. This process wasrepeated with BlueSky Armor™ 1047 Clear Top Coat and the wet slide wasplaced in the Nicolet FTIR spectrometer and cured at a low radiant fluxof 10 mW/cm² and real time conversion data was collected as shown inFIG. 10 and Table 1. This process was repeated with BlueSky Armor™ 1047Clear Top Coat and the wet slide was placed in the Nicolet FTIRspectrometer and cured at a low radiant flux of 20 mW/cm² and real timeconversion data was collected as shown in FIG. 10 and Table 1.

BlueSky Armor™ 1057 Clear Top Coat uncured material was placed onCorning 2947-75X25 Soda Lime Glass Plain Microscope Slide that was 75 mmLength×25 mm Width×0.90-1.10 mm thick. The uncured material was drawndown across the slide with an AccuDyne #100 wire-wound metering rod, sothat the slide was completely and uniformly covered with the wetmaterial to a thickness of about 0.25 mm. Next, the wet slide was placedin the Nicolet FTIR spectrometer and cured at a low radiant flux of 2.5mW/cm² and real time conversion data was collected as shown in FIG. 11and Table 1. This process was repeated with BlueSky Armor™ 1057 ClearTop Coat and the wet slide was placed in the Nicolet FTIR spectrometerand cured at a low radiant flux of 5 mW/cm² and real time conversiondata was collected as shown in FIG. 11 and Table 1. This process wasrepeated with BlueSky Armor™ 1057 Clear Top Coat and the wet slide wasplaced in the Nicolet FTIR spectrometer and cured at a low radiant fluxof 10 mW/cm² and real time conversion data was collected as shown inFIG. 11 and Table 1. This process was repeated with BlueSky Armor™ 1057Clear Top Coat and the wet slide was placed in the Nicolet FTIRspectrometer and cured at a low radiant flux of 20 mW/cm² and real timeconversion data was collected as shown in FIG. 11 and Table 1.

TABLE 1 Acrylate conversion for each product at each intensity.Formulation 2.5 mW/cm² 5 mW/cm² 10 mW/cm² 20 mW/cm² MSI 1007 80% 84% 92%94% MSI 1027 81% 88% 96% 95% MSI 1047 76% 82% 91% 90% MSI 1057 80% 86%91% 90%

Next, the time to tack free curing in an oxygen environment at varyinglow radiant flux energies was determined for each of the followingBlueSky Armor™ 1007 Clear Top Coat, BlueSky Armor™, 1027 Clear Top Coat,BlueSky Armor™ 1047 Clear Knife Grade Filler, and BlueSky Armor™ 1057Laminating Resin. The low radiant flux energies at the surface of thecuring were tested were 2.5 mW/cm², 5 mW/cm², 10 mW/cm², and 20 mW/cm².The same energy sources described above were used.

BlueSky Armor™ 1007 Clear Top Coat uncured material was placed onCorning 2947-75X25 Soda Lime Glass Plain Microscope Slide that was 75 mmLength×25 mm Width×0.90-1.10 mm thick. The uncured material was drawndown across the slide with an AccuDyne #100 wire-wound metering rod, sothat the slide was completely and uniformly covered with the wetmaterial to a thickness of about 0.25 mm. Next, the wet slide was curedat a low radiant flux at the surface of 2.5 mW/cm² and the quality ofcure was checked every 15 s by touching the surface of the sample. Ifthe sample was marred in anyway the cure was considered tacky. Thisprocess was repeated at 5 mW/cm², 10 mW/cm², and 20 mW/cm² results areshown in Table 2. The process was also repeated for 1027 Clear Top Coat,BlueSky Armor™ 1047 Clear Knife Grade Filler, and BlueSky Armor™ 1057Laminating Resin at the low radiant flux energies at the surface of thecuring were tested were 2.5 mW/cm², 5 mW/cm², 10 mW/cm², and 20 mW/cm²and results shown in Table 2.

TABLE 2 Time to tack free Formulation 2.5 mW/cm² 5 mW/cm² 10 mW/cm² 20mW/cm² MSI 1007 >5 min 2 min 70 s 40 s MSI 1027 >5 min 2 min 90 s 40 sMSI 1047 >5 min 105 s 80 s 50 s MSI 1057 >5 min 2 min 90 s 40 s

Next, the viscosity, tensile properties, flexural properties, shorehardness and solvent resistance were measured for the BlueSky Armor™1007 Clear Top Coat, BlueSky Armor™, 1027 Clear Top Coat, BlueSky Armor™1047 Clear Knife Grade Filler, and BlueSky Armor™ 1057 Laminating Resinfrom MSI Coatings, Inc. out of Boulder, Colorado.

The viscosity was measured with a model DV-II Brookfield viscometerusing #31 or #18 spindle at 25° C. using the small sample adapter withvolumes of about 5 mL to about 16 mL where appropriate. The tensileproperties were obtained from fabricating samples from laminating Teflonmolds that had a gauge length of 35 mm, width of 6 mm and thickness of 1mm between glass slides and cured with a 395-410 nm 150 W LED light at10 mW/cm² for 2 minutes. Samples were pulled at 10 mm/min following ASTMD638-10 standard, which is hereby incorporated by reference. The resultsare shown in Table 3.

The flexural properties were obtained and made from laminating Teflonmolds that having a gauge length of 35 mm, width of 6 mm and thicknessof 1 mm between glass slides teflon molds that had dimensions of22×2.2×2.5 mm and cured at a wavelength of about 395 nm to about 410 nmwith a 150W LED light at low radiant energy flux at the surface of 10mW/cm² for 2 minutes. Samples were bent at 1 mm/min following the ASTMD790-03 standard, which is hereby incorporated by reference. The resultsare shown in Table 3. The shore hardness were obtained from samplesdrawn down with an AccuDyne #100 wire wound bar. Shore hardness wasmeasured with Shore A and D durometers. The results are shown in Table3. The solvent resistance was obtained with MEK double rubs performedusing ASTM D540-93 standard, which is hereby incorporate by reference.

TABLE 3 Summary of characteristic data. Standard deviations are inparentheses. MSI MSI MSI MSI Vinyl Property 1007 1027 1047 1057 esterEpoxy Viscosity at 100 32 Paste 300 530-1300 800  25 C. (cps) (30-3 rpm)Tensile 750 160 1400 900 1160 1500 Modulus (mPa) (100) (10) (100) (100)(70) (50) Tensile 29 14 23 35 40 60 Strength (mPa) (7) (2) (4) (5) (3)(5) Tensile 6 20 3 8 6 4 Elongation (2) (5) (1) (2) (2) (2) Flexural1050 150 1250 1100 1200 1650 Modulus (mPa) (100) (20) (70) (90) (150)(200) Flexural 39 5.5 46 41 46 61 Strength (mPa) (4) (1) (4) (3) (6)(10) Flexural 17 35 16 18 27 30 Elongation (3) (10) (5) (8) (8) (1) MEKdouble  200+ 200+ 200+  200+ 1 200+ rubs Shore hardness 73D 60D 75D 82D80D 84

Although the present disclosure describes components and functionsimplemented in the aspects, embodiments, and/or configurations withreference to particular standards and protocols, the aspects,embodiments, and/or configurations are not limited to such standards andprotocols. Other similar standards and protocols not mentioned hereinare in existence and are considered to be included in the presentdisclosure. Moreover, the standards and protocols mentioned herein andother similar standards and protocols not mentioned herein areperiodically superseded by faster or more effective equivalents havingessentially the same functions. Such replacement standards and protocolshaving the same functions are considered equivalents included in thepresent disclosure.

The present disclosure, in various aspects, embodiments, and/orconfigurations, includes components, methods, processes, systems and/orapparatus substantially as depicted and described herein, includingvarious aspects, embodiments, configurations embodiments, subcombinations, and/or subsets thereof. Those of skill in the art willunderstand how to make and use the disclosed aspects, embodiments,and/or configurations after understanding the present disclosure. Thepresent disclosure, in various aspects, embodiments, and/orconfigurations, includes providing devices and processes in the absenceof items not depicted and/or described herein or in various aspects,embodiments, and/or configurations hereof, including in the absence ofsuch items as may have been used in previous devices or processes, e.g.,for improving performance, achieving ease and/or reducing cost ofimplementation.

The foregoing discussion has been presented for purposes of illustrationand description. The foregoing is not intended to limit the disclosureto the form or forms disclosed herein. In the foregoing description forexample, various features of the disclosure are grouped together in oneor more aspects, embodiments, and/or configurations for the purpose ofstreamlining the disclosure. The features of the aspects, embodiments,and/or configurations of the disclosure may be combined in alternateaspects, embodiments, and/or configurations other than those discussedabove. This method of disclosure is not to be interpreted as reflectingan intention that the claims require more features than are expresslyrecited in each claim. Rather, as the following claims reflect,inventive aspects lie in less than all features of a single foregoingdisclosed aspect, embodiment, and/or configuration. Thus, the followingclaims are hereby incorporated into this description, with each claimstanding on its own as a separate preferred embodiment of thedisclosure.

Moreover, though the description has included a description of one ormore aspects, embodiments, and/or configurations and certain variationsand modifications, other variations, combinations, and modifications arewithin the scope of the disclosure, e.g., as may be within the skill andknowledge of those in the art, after understanding the presentdisclosure. It is intended to obtain rights which include alternativeaspects, embodiments, and/or configurations to the extent permitted,including alternate, interchangeable and/or equivalent structures,functions, ranges or steps to those claimed, whether or not suchalternate, interchangeable and/or equivalent structures, functions,ranges or steps are disclosed herein, and without intending to publiclydedicate any patentable subject matter.

1.-94. (canceled)
 95. A method of repairing at least a portion of adamaged pipe, comprising: preparing at least a portion of the damagedpipe for repair; arranging a composite material that is substantiallysaturated with a VOC free low radiant flux UV curable composition on atleast a portion of the damaged pipe; applying an energy source having awavelength in a range from about 360 nm to about 420 nm and a radiantflux at a surface of the substantially saturated composite material ofabout 100 mW/cm² or less to cure at least a portion of the substantiallysaturated composite material, wherein the VOC free low radiant flux UVcurable composition comprises: an acrylate monomers/oligomers; a thiolmonomers/oligomers; a photo initiator; and a radical inhibitor.
 96. Themethod of claim 95, wherein the wavelength is about 390 nm.
 97. Themethod of claim 95, wherein the radiant flux at the surface of thesubstantially saturated composite material is about 50 mW/cm² or less.98. The method of claim 95, wherein the radiant flux at the surface ofthe substantially saturated composite material is about 25 mW/cm² orless.
 99. The method of claim 95, wherein the radiant flux at thesurface of the substantially saturated composite material is about 10mW/cm² or less.
 100. The method of claim 95, wherein the radiant flux atthe surface of the substantially saturated composite material is about 5mW/cm² or less.
 101. The method of claim 95, wherein the radiant flux atthe surface of the substantially saturated composite material isprovided in a roll.
 102. The method of claim 95, wherein thesubstantially saturated composite material is provided as a patch havingone or more layers.
 103. The method of claim 95, wherein thesubstantially saturated composite material is provided as apre-impregnated composite material.
 104. The method of claim 103,wherein the pre-impregnated composite material comprises one or morelayers of a composite material.
 105. The method of claim 104, whereinthe composite material comprises one or more of a fiberglass material,cellulose fiber material, carbon fiber material, polymer fiber material,metallic fiber material, silicon carbide fiber material, and mineralfiber material.
 106. The method of claim 104, wherein the compositematerial comprises a fiberglass material.
 107. The method of claim 104,wherein the arranging of the composite material that is substantiallysaturated with a VOC free low radiant flux UV curable composition on atleast a portion of the damaged pipe is arranged on an interior orexterior surface of the damaged pipe.
 108. The method of claim 95,wherein the VOC free low radiant flux UV curable composition comprisesat least ninety-five (95%) percent solids.
 109. The method of claim 95,wherein the VOC free low radiant flux UV curable composition comprisesat least ninety-six (96%) percent solids.
 110. The method of claim 95,wherein the VOC free low radiant flux UV curable composition comprisesat least ninety-seven (97%) percent solids.
 111. The method of claim 95,wherein the VOC free low radiant flux UV curable composition comprisesat least ninety-eight (98%) percent solids.
 112. A method of repairingat least a portion of a damaged pipe, comprising: preparing a portion ofthe pipe for repair; applying a VOC free low radiant flux UV curablecomposition to a composite material to substantially saturate thecomposite material, wherein the composite material has internal surface,an external surface, a first end, a second end separated from the firstend, and a lumen that extends from the first end to the second end;arranging an inflatable member in the lumen of the saturated compositematerial; inflating a portion of the inflatable member to expand thestatured composite material to be at least substantially adjacent to aninterior surface of the pipe; applying an energy source having awavelength in a range from about 360 nm to about 420 nm and a radiantflux at a surface of the saturated composite material of about 100mW/cm² or less to at least partially cure the saturated compositematerial; wherein the VOC free low radiant flux UV curable compositioncomprises: an acrylate monomers/oligomers; a thiol monomers/oligomers; aphoto initiator; and a radical inhibitor.
 113. The method of claim 113,wherein the composite material comprises one or more of a fiberglassmaterial, cellulose fiber material, carbon fiber material, polymer fibermaterial, metallic fiber material, silicon carbide fiber material, andmineral fiber material.
 114. A method of repairing at least a portion ofa damaged pipe, comprising: preparing a portion of the pipe for repair;applying a VOC free low radiant flux UV curable composition to acomposite material to substantially saturate the composite material,wherein the composite material has internal surface, an externalsurface, a first end, a second end separated from the first end, and alumen that extends from the first end to the second end; arranging aportion of the statured composite material to be at least substantiallyadjacent to an interior surface of the pipe; applying an energy sourcehaving a wavelength in a range from about 360 nm to about 420 nm and aradiant flux at a surface of the saturated composite material of about100 mW/cm² or less to at least partially cure the saturated compositematerial, wherein the VOC free low radiant flux UV curable compositioncomprises: an acrylate monomers/oligomers; a thiol monomers/oligomers; aphoto initiator; and a radical inhibitor.
 115. The method of claim 114,wherein the composite material comprises one or more of a fiberglassmaterial, cellulose fiber material, carbon fiber material, polymer fibermaterial, metallic fiber material, silicon carbide fiber material, andmineral fiber material.